ITQ-26, new crystalline microporous material

ABSTRACT

ITQ-26 (INSTITUTO DE TECNOLOOIA QUIMICA number 26) is a new crystalline microporous material with a framework of tetrahedral atoms connected by atoms capable of bridging the tetrahedral atoms, the tetrahedral atom framework being defined by the interconnections between the tetrahedrally coordinated atoms in its framework, ITQ-26 can be prepared in silicate compositions with an organic structure directing agent. It has a unique X-ray diffraction pattern, which identifies it as a new material. ITQ-26 is stable to calcination in air, absorbs hydrocarbons, and is catalytically active for hydrocarbon conversion.

BACKGROUND OF THE INVENTION

Microporous materials, including zeolites and silicoaluminophosphates,are widely used in the petroleum industry as absorbents, catalysts andcatalyst supports. Their crystalline structures consist ofthree-dimensional frameworks containing uniform pore openings, channelsand internal cages of dimensions (<20 Å) similar to most hydrocarbons.The composition of the frameworks can be such that they are anionic,which requires the presence of non-framework cations to balance thenegative charge. These non-framework cations, such as alkali or alkalineearth metal cations, are exchangeable, either entirely or partially withanother type of cation utilizing ion exchange techniques in aconventional manner. If these non-framework cations are converted to theproton form by, for example, acid treatments or exchange with ammoniumcations followed by calcination to remove the ammonia, it imparts thematerial with Brønsted acid sites having catalytic activity. Thecombination of acidity and restricted pore openings gives thesematerials catalytic properties unavailable with other materials due totheir ability to exclude or restrict some of the products, reactants,and/or transition states in many reactions. Non-reactive materials, suchas pure silica and aluminophosphate frameworks are also useful and canbe used in absorption and separation processes of liquids, gases, andreactive molecules such as alkenes.

The family of crystalline microporous compositions known as molecularsieves, which exhibit the ion-exchange and/or adsorption characteristicsof zeolites are the aluminophosphates, identified by the acronym AlPO,and substituted aluminophosphates as disclosed in U.S. Pat. Nos.4,310,440 and 4,440,871. U.S. Pat. No. 4,440,871 discloses a class ofsilica aluminophosphates, which are identified by the acronym SAPO andwhich have different structures as identified by their X-ray diffractionpattern. The structures are identified by a numerical number after AlPO,SAPO, MeAPO (Me=metal), etc. (Flanigen et al., Proc. 7th Int. ZeoliteConf., p. 103 (1986) and may include Al and P substitutions by B, Si,Be, Mg, Ge, Zn, Fe, Co, Ni, etc. The present invention is a newmolecular sieve having a unique framework structure.

ExxonMobil and others extensively use various microporous materials,such as faujasite, mordenite, and ZSM-5 in many commercial applications.Such applications include reforming, cracking, hydrocracking,alkylation, oligomerization, dewaxing and isomerization. Any newmaterial has the potential to improve the catalytic performance overthose catalysts presently employed.

There are currently over 150 known microporous framework structures astabulated by the International Zeolite Association. There exists theneed for new structures, having different properties than those of knownmaterials, for improving the performance of many hydrocarbon processes.Each structure has unique pore, channel and cage dimensions, which givesits particular properties as described above. ITQ-26 is a new frameworkmaterial.

SUMMARY OF THE INVENTION

ITQ-26 (INSTITUTO DE TECNOLOGÍA QUÍMICA number 26) is a new crystallinemicroporous material having a framework of tetrahedral atoms connectedby bridging atoms, the tetrahedral atom framework being defined by theinterconnections between the tetrahedrally coordinated atoms in itsframework. ITQ-26 is stable to calcination in air, absorbs hydrocarbons,and is catalytically active for hydrocarbon conversion.

In one embodiment, the present invention is directed to a newcrystalline material that is a silicate compound having a compositionmR:aX₂O₃:YO₂.nH₂O where R is an organic compound, X is any metal capableof tetrahedral coordination such as one or more of B, Ga, Al, Fe, Li,Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, morepreferably one or more trivalent metals capable of tetrahedralcoordination, and even more preferably one or more of the elements B,Ga, Al, and Fe, and Y is Si alone or in combination with any othertetravalent metal capable of tetrahedral coordination such as Ge and Tiand where m=0.01-1, a=0.00-0.2, and n=0-10 and having a uniquediffraction pattern as given in Table 2.

In a more specific embodiment, the present invention is directed to acalcined crystalline silicate compound that has a compositionaX₂O₃:YO₂.nH₂O, where X is any metal capable of tetrahedral coordinationsuch as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn,As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metalscapable of tetrahedral coordination, and even more preferably one ormore of the elements B, Ga, Al, and Fe, and Y is Si alone or incombination with any other tetravalent metal capable of tetrahedralcoordination such as Ge and Ti and where a=0.00-0.2 and n=0-10 andhaving a unique diffraction pattern as given in Table 3.

The present invention also includes a method of synthesizing acrystalline silicate compound having the diffraction pattern similar toTable 2, by mixing together a source of silica, organic structuredirecting agent (SDA), water, and optional metal and heating at atemperature and time sufficient to crystallize the silicate.

The invention includes the use of ITQ-26 to separate hydrocarbons from ahydrocarbon containing stream.

The invention also includes the use of ITQ-26 as a hydrocarbonconversion catalyst for converting an organic feedstock to conversionproducts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representation of1,3-bis-(triethylphosphonium-methyl)-benzene the organic structuredirecting agent (SDA).

FIG. 2 shows the framework structure of ITQ-26 showing only thetetrahedral atoms. There is one unit cell, whose edges are defined bythe gray box.

FIG. 3 shows the X-ray diffraction pattern of as-synthesized ITQ-26.

FIG. 4 shows the X-ray diffraction pattern of calcined/dehydratedITQ-26.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is a new structure of crystalline material. Aswith any porous crystalline material, the structure of ITQ-26 can bedefined by the interconnections between the tetrahedrally coordinatedatoms in its framework. In particular, ITQ-26 has a framework oftetrahedral (T) atoms connected by bridging atoms, wherein thetetrahedral atom framework is defined by connecting the nearesttetrahedral (T) atoms in the manner given in Table 1.

TABLE 1 ITQ-26 tetrahedral atom interconnections T atom Connected to: T1T2, T5, T56, T68 T2 T1, T4, T57, T69 T3 T4, T17, T24, T43 T4 T2, T3, T6,T75 T5 T1, T7, T116, T120 T6 T4, T20, T27, T44 T7 T5, T14, T34, T70 T8T9, T12, T53, T65 T9 T8, T11, T54, T66 T10 T11, T17, T24, T49 T11 T9,T10, T13, T72 T12 T8, T14, T111, T115 T13 T11, T20, T27, T50 T14 T7,T12, T40, T67 T15 T16, T19, T62, T71 T16 T15, T18, T63, T72 T17 T3, T10,T18, T31 T18 T16, T17, T20, T69 T19 T15, T21, T106, T110 T20 T6, T13,T18, T32 T21 T19, T28, T52, T73 T22 T23, T26, T59, T74 T23 T22, T25,T60, T75 T24 T3, T10, T25, T37 T25 T23, T24, T27, T66 T26 T22, T28,T101, T105 T27 T6, T13, T25, T38 T28 T21, T26, T46, T76 T29 T30, T33,T56, T68 T30 T29, T32, T57, T69 T31 T17, T32, T43, T49 T32 T20, T30,T31, T63 T33 T29, T34, T95, T100 T34 T7, T33, T40, T58 T35 T36, T39,T53, T65 T36 T35, T38, T54, T66 T37 T24, T38, T43, T49 T38 T27, T36,T37, T60 T39 T35, T40, T89, T94 T40 T14, T34, T39, T55 T41 T42, T45,T59, T74 T42 T41, T44, T60, T75 T43 T3, T31, T37, T44 T44 T6, T42, T43,T57 T45 T41, T46, T83, T88 T46 T28, T45, T52, T61 T47 T48, T51, T62, T71T48 T47, T50, T63, T72 T49 T10, T31, T37, T50 T50 T13, T48, T49, T54 T51T47, T52, T77, T82 T52 T21, T46, T51, T64 T53 T8, T35, T54, T55 T54 T9,T36, T50, T53 T55 T40, T53, T100, T135 T56 T1, T29, T57, T58 T57 T2,T30, T44, T56 T58 T34, T56, T94, T133 T59 T22, T41, T60, T61 T60 T23,T38, T42, T59 T61 T46, T59, T82, T131 T62 T15, T47, T63, T64 T63 T16,T32, T48, T62 T64 T52, T62, T88, T129 T65 T8, T35, T66, T67 T66 T9, T25,T36, T65 T67 T14, T65, T120, T127 T68 T1, T29, T69, T70 T69 T2, T18,T30, T68 T70 T7, T68, T115, T125 T71 T15, T47, T72, T73 T72 T11, T16,T48, T71 T73 T21, T71, T105, T123 T74 T22, T41, T75, T76 T75 T4, T23,T42, T74 T76 T28, T74, T110, T121 T77 T51, T78, T123, T131 T78 T77, T80,T124, T132 T79 T80, T91, T97, T113 T80 T78, T79, T81, T136 T81 T80, T93,T99, T114 T82 T51, T61, T88, T105 T83 T45, T84, T121, T129 T84 T83, T86,T122, T130 T85 T86, T91, T97, T118 T86 T84, T85, T87, T134 T87 T86, T93,T99, T119 T88 T45, T64, T82, T110 T89 T39, T90, T127, T133 T90 T89, T92,T128, T134 T91 T79, T85, T92, T103 T92 T90, T91, T93, T132 T93 T81, T87,T92, T104 T94 T39, T58, T100, T120 T95 T33, T96, T125, T135 T96 T95,T98, T126, T136 T97 T79, T85, T98, T108 T98 T96, T97, T99, T130 T99 T81,T87, T98, T109 T100 T33, T55, T94, T115 T101 T26, T102, T123, T131 T102T101, T104, T124, T132 T103 T91, T104, T113, T118 T104 T93, T102, T103,T128 T105 T26, T73, T82, T110 T106 T19, T107, T121, T129 T107 T106,T109, T122, T130 T108 T97, T109, T113, T118 T109 T99, T107, T108, T126T110 T19, T76, T88, T105 T111 T12, T112, T125, T135 T112 T111, T114,T126, T136 T113 T79, T103, T108, T114 T114 T81, T112, T113, T124 T115T12, T70, T100, T120 T116 T5, T117, T127, T133 T117 T116, T119, T128,T134 T118 T85, T103, T108, T119 T119 T87, T117, T118, T122 T120 T5, T67,T94, T115 T121 T76, T83, T106, T122 T122 T84, T107, T119, T121 T123 T73,T77, T101, T124 T124 T78, T102, T114, T123 T125 T70, T95, T111, T126T126 T96, T109, T112, T125 T127 T67, T89, T116, T128 T128 T90, T104,T117, T127 T129 T64, T83, T106, T130 T130 T84, T98, T107, T129 T131 T61,T77, T101, T132 T132 T78, T92, T102, T131 T133 T58, T89, T116, T134 T134T86, T90, T117, T133 T135 T55, T95, T111, T136 T136 T80, T96, T112, T135

Tetrahedral atoms are those capable of having tetrahedral coordination,including one or more of, but not limiting, lithium, beryllium, boron,magnesium, aluminum, silicon, phosphorous, titanium, chromium,manganese, iron, cobalt, nickel, copper, zinc, zirconium, gallium,germanium, arsenic, indium, tin, and antimony.

In one embodiment, this new crystalline silicate compound has acomposition mR:aX₂O₃:YO₂.nH₂O where R is an organic compound, and X isany metal capable of tetrahedral coordination such as one or more of B,Al, Ga, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, andZr, more preferably one or more trivalent metals capable of tetrahedralcoordination, and even more preferably one or more of the elements B,Ga, Al, and Fe, and Y is Si alone or in combination with any othertetravalent metal capable of tetrahedral coordination such as Ge and Tiand where m=0.01-1, a=0.00-0.2, and n=0-10. This compound has the uniquediffraction pattern given in Table 2 and shown in FIG. 3.

TABLE 2 X-ray diffraction lines for as-synthesized ITQ-26 relative int.d (Å) (%) 13.8-13.0 60-100 12.3-11.6 5-40 9.09-8.73 30-80  6.55-6.375-50 4.76-4.66 5-50 4.49-4.40 20-70  4.20-4.12 50-100 3.81-3.75 5-503.69-3.63 5-50 3.36-3.31 30-80  2.998-2.959 5-40 2.846-2.811 5-402.624-2.594 5-40 2.503-2.476 5-40 2.366-2.342 5-40

Other embodiments of the new structure include a calcined compound ofcomposition aX₂O₂:YO₂.nH₂O, where X is any metal capable of tetrahedralcoordination such as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr,Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or moretrivalent metals capable of tetrahedral coordination, and even morepreferably one or more of the elements B, Ga, Al, Fe, and Y is Si aloneor in combination with any other tetravalent metal capable oftetrahedral coordination such as Ge and Ti and where a=0.00-0.2, andn=0-10. This compound has the unique diffraction pattern given in Table3 and FIG. 4.

TABLE 3 X-ray diffraction lines for calcined/dehydrated ITQ-26 d (Å)relative int. (%) 13.7-13.0 60-100 12.2-11.6 20-70  9.63-9.27 1-109.03-8.72 20-70  6.55-6.39 1-10 5.01-4.91 1-10 4.75-4.66 1-20 4.50-4.421-20 4.39-4.32 1-10 4.21-4.14 1-20 4.17-4.10 1-20 3.82-3.76 1-103.70-3.65 1-20 3.37-3.32 1-20 3.33-3.29 1-10 3.14-3.10 1-10

This new compound is made by the method of mixing together a source ofsilica, organic structure directing agent (SDA), water, and optionalsource of metal and heating at a temperature and time sufficient tocrystallize the silicate. The method is described below.

The synthetic porous crystalline material of this invention, ITQ-26, isa crystalline phase which has a unique 3-dimensional channel systemcomprising intersecting 12-membered rings of tetrahedrally coordinatedatoms. The 12-membered ring channels have cross-sectional dimensionsbetween the bridging oxygen atoms of about 7.8 Ångströms by about 6.8Ångströms along one direction and about 7.1 Ångströms by about 6.6Ångströms along the other two directions.

Variations in the X-ray diffraction pattern may occur between thedifferent chemical composition forms of ITQ-26, such that the exactITQ-26 structure can vary due its particular composition and whether ornot it has been calcined and rehydrated.

In the as-synthesized form ITQ-26 has a characteristic X-ray diffractionpattern, the essential lines of which are given in Table 2 measured withCu Kα radiation. Variations occur as a function of specific compositionand its loading in the structure. For this reason the intensities andd-spacings are given as ranges.

The ITQ-26 material of the present invention may be calcined to removethe organic templating agent without loss of crystallinity. This isuseful for activating the material for subsequent absorption of otherguest molecules such as hydrocarbons. The essential lines, whichuniquely define calcined/dehydrated ITQ-26 are shown in Table 3 measuredwith synchrotron radiation. Variations occur as a function of specificcomposition, temperature and the level of hydration in the structure.For this reason the intensities and d-spacings are given as ranges.

In addition, to describing the structure of ITQ-26 by theinterconnections of the tetrahedral atoms as in Table 1 above, it may bedefined by its unit cell, which is the smallest repeating unitcontaining all the structural elements of the material. The porestructure of ITQ-26 is illustrated in FIG. 2 (which shows only thetetrahedral atoms) down the direction of the 12-membered ring channels.There is a single unit cell unit in FIG. 2, whose limits are defined bythe box. Table 4 lists the typical positions of each tetrahedral atom inthe unit cell in units of Ångströms. Each tetrahedral atom is bonded tobridging atoms, which are also bonded to adjacent tetrahedral atoms.Tetrahedral atoms are those capable of having tetrahedral coordination,including one or more of, but not limiting, lithium, beryllium, boron,magnesium, aluminum, silicon, phosphorous, titanium, chromium,manganese, iron, cobalt, nickel, copper, zinc, zirconium, gallium,germanium, arsenic, indium, tin, and antimony. Bridging atoms are thosecapable of connecting two tetrahedral atoms, examples which include, butnot limiting, oxygen, nitrogen, fluorine, sulfur, selenium, and carbonatoms.

In the case of oxygen, it is also possible that the bridging oxygen isalso connected to a hydrogen atom to form a hydroxyl group (—OH—). Inthe case of carbon it is also possible that the carbon is also connectedto two hydrogen atoms to form a methylene group (—CH₂—). For example,bridging methylene groups have been seen in the zirconium diphosphonate,MIL-57. See: C. Serre, G. Férey, J. Mater. Chem. 12, p. 2367 (2002).Bridging sulfur and selenium atoms have been seen in the UCR-20-23family of microporous materials. See: N. Zheng, X. Bu, B. Wang, P. Feng,Science 298, p. 2366 (2002). Bridging fluorine atoms have been seen inlithium hydrazinium fluoroberyllate, which has the ABW structure type.See: M. R. Anderson, I. D. Brown, S. Vilminot, Acta Cryst. B29, p. 2626(1973). Since tetrahedral atoms may move about due to other crystalforces (presence of inorganic or organic species, for example), or bythe choice of tetrahedral and bridging atoms, a range of ±1.0 Ångströmis implied for the x and y coordinate positions and a range of ±0.5Ångström for the z coordinate positions.

TABLE 4 Positions of tetrahedral (T) atoms for the ITQ-26 structure.Values, in units of Ångströms, are approximate and are typical when T =silicon and the bridging atoms are oxygen. Atom x (Å) y (Å) z (Å) T11.559 8.591 1.558 T2 1.559 5.478 1.559 T3 1.559 1.559 5.056 T4 2.7912.791 2.490 T5 2.352 11.023 3.307 T6 1.531 1.531 0.000 T7 0.000 11.8445.084 T8 25.191 18.159 1.558 T9 25.191 21.272 1.559 T10 25.191 25.1915.056 T11 23.959 23.959 2.490 T12 24.398 15.727 3.307 T13 25.219 25.2190.000 T14 0.000 14.906 5.084 T15 18.159 1.559 1.558 T16 21.272 1.5591.559 T17 25.191 1.559 5.056 T18 23.959 2.791 2.490 T19 15.727 2.3523.307 T20 25.219 1.531 0.000 T21 14.906 0.000 5.084 T22 8.591 25.1911.558 T23 5.478 25.191 1.559 T24 1.559 25.191 5.056 T25 2.791 23.9592.490 T26 11.023 24.398 3.307 T27 1.531 25.219 0.000 T28 11.844 0.0005.084 T29 25.191 8.591 11.672 T30 25.191 5.478 11.671 T31 25.191 1.5598.174 T32 23.959 2.791 10.740 T33 24.398 11.023 9.922 T34 0.000 11.8448.146 T35 1.559 18.159 11.672 T36 1.559 21.272 11.671 T37 1.559 25.1918.174 T38 2.791 23.959 10.740 T39 2.352 15.727 9.922 T40 0.000 14.9068.146 T41 8.591 1.559 11.672 T42 5.478 1.559 11.671 T43 1.559 1.5598.174 T44 2.791 2.791 10.740 T45 11.023 2.352 9.922 T46 11.844 0.0008.146 T47 18.159 25.191 11.672 T48 21.272 25.191 11.671 T49 25.19125.191 8.174 T50 23.959 23.959 10.740 T51 15.727 24.398 9.922 T52 14.9060.000 8.146 T53 25.191 18.159 11.672 T54 25.191 21.272 11.671 T55 24.39815.727 9.922 T56 1.559 8.591 11.672 T57 1.559 5.478 11.671 T58 2.35211.023 9.922 T59 8.591 25.191 11.672 T60 5.478 25.191 11.671 T61 11.02324.398 9.922 T62 18.159 1.559 11.672 T63 21.272 1.559 11.671 T64 15.7272.352 9.922 T65 1.559 18.159 1.558 T66 1.559 21.272 1.559 T67 2.35215.727 3.307 T68 25.191 8.591 1.558 T69 25.191 5.478 1.559 T70 24.39811.023 3.307 T71 18.159 25.191 1.558 T72 21.272 25.191 1.559 T73 15.72724.398 3.307 T74 8.591 1.559 1.558 T75 5.478 1.559 1.559 T76 11.0232.352 3.307 T77 14.934 21.966 8.173 T78 14.934 18.853 8.174 T79 14.93414.934 11.671 T80 16.166 16.166 9.105 T81 14.906 14.906 6.615 T82 13.37525.219 11.699 T83 11.816 4.784 8.173 T84 11.816 7.897 8.174 T85 11.81611.816 11.671 T86 10.584 10.584 9.105 T87 11.844 11.844 6.615 T88 13.3751.531 11.699 T89 4.784 14.934 8.173 T90 7.897 14.934 8.174 T91 11.81614.934 11.671 T92 10.584 16.166 9.105 T93 11.844 14.906 6.615 T94 1.53113.375 11.699 T95 21.966 11.816 8.173 T96 18.853 11.816 8.174 T97 14.93411.816 11.671 T98 16.166 10.584 9.105 T99 14.906 11.844 6.615 T10025.219 13.375 11.699 T101 11.816 21.966 5.057 T102 11.816 18.853 5.056T103 11.816 14.934 1.559 T104 10.584 16.166 4.125 T105 13.375 25.2191.531 T106 14.934 4.784 5.057 T107 14.934 7.897 5.056 T108 14.934 11.8161.559 T109 16.166 10.584 4.125 T110 13.375 1.531 1.531 T111 21.96614.934 5.057 T112 18.853 14.934 5.056 T113 14.934 14.934 1.559 T11416.166 16.166 4.125 T115 25.219 13.375 1.531 T116 4.784 11.816 5.057T117 7.897 11.816 5.056 T118 11.816 11.816 1.559 T119 10.584 10.5844.125 T120 1.531 13.375 1.531 T121 11.816 4.784 5.057 T122 11.816 7.8975.056 T123 14.934 21.966 5.057 T124 14.934 18.853 5.056 T125 21.96611.816 5.057 T126 18.853 11.816 5.056 T127 4.784 14.934 5.057 T128 7.89714.934 5.056 T129 14.934 4.784 8.173 T130 14.934 7.897 8.174 T131 11.81621.966 8.173 T132 11.816 18.853 8.174 T133 4.784 11.816 8.173 T134 7.89711.816 8.174 T135 21.966 14.934 8.173 T136 18.853 14.934 8.174

The complete structure of ITQ-26 is built by connecting multiple unitcells as defined above in a fully-connected three-dimensional framework.The tetrahedral atoms in one unit cell are connected to certaintetrahedral atoms in all of its adjacent unit cells. While Table 1 liststhe connections of all the tetrahedral atoms for a given unit cell ofITQ-26, the connections may not be to the particular atom in the sameunit cell but to an adjacent unit cell. All of the connections listed inTable 1 are such that they are to the closest tetrahedral (T) atoms,regardless of whether they are in the same unit cell or in adjacent unitcells.

Although the Cartesian coordinates given in Table 4 may accuratelyreflect the positions of tetrahedral atoms in an idealized structure,the true structure can be more accurately described by the connectivitybetween the framework atoms as shown in Table 1 above.

Another way to describe this connectivity is by the use of coordinationsequences as applied to microporous frameworks by W. M. Meier and H. J.Moeck, in the Journal of Solid State Chemistry 27, p. 349 (1979). In amicroporous framework, each tetrahedral atom, No, (T-atom) is connectedto N₁=4 neighboring T-atoms through bridging atoms (typically oxygen).These neighboring T-atoms are then connected to N₂ T-atoms in the nextshell. The N₂ atoms in the second shell are connected to N₃ T-atoms inthe third shell, and so on. Each T-atom is only counted once, such that,for example, if a T-atom is in a 4-membered ring, at the fourth shellthe No atom is not counted second time, and so on. Using thismethodology, a coordination sequence can be determined for each uniqueT-atom of a 4-connected net of T-atoms. The following line lists themaximum number of T-atoms for each shell.N₀=1 N₁≦4 N₂≦12 N₃≦36 N_(k)≦4·3^(k-1)

TABLE 5 Coordination sequence for ITQ-26 structure. atom atom numberlabel coordination sequence 1 T(1) 4 9 18 31 47 66 94 127 159 188 226287 345 2 T(2) 4 9 17 29 44 68 97 125 154 190 240 292 338 3 T(3) 4 9 1830 42 60 89 126 162 188 222 281 349 4 T(4) 4 12 18 27 48 69 94 124 160201 237 285 330 5 T(5) 4 12 17 30 46 67 90 124 158 186 230 279 344 6T(6) 4 11 20 24 36 72 110 126 136 182 256 306 326 7 T(7) 4 11 20 28 4270 100 120 146 186 232 291 349

One way to determine the coordination sequence for a given structure isfrom the atomic coordinates of the framework atoms using the computerprogram zeoTsites (see G. Sastre, J. D. Gale, Microporous and mesoporousMaterials 43, p. 27 (2001).

The coordination sequence for the ITQ-26 structure is given in Table 5.The T-atom connectivity as listed in Table 1 and is for T-atoms only.Bridging atoms, such as oxygen usually connects the T-atoms. Althoughmost of the T-atoms are connected to other T-atoms through bridgingatoms, it is recognized that in a particular crystal of a materialhaving a framework structure, it is possible that a number of T-atomsmay not connected to one another. Reasons for non-connectivity include,but are not limited by; T-atoms located at the edges of the crystals andby defects sites caused by, for example, vacancies in the crystal. Theframework listed in Table 1 and Table 5 is not limited in any way by itscomposition, unit cell dimensions or space group symmetry.

While the idealized structure contains only 4-coordinate T-atoms, it ispossible under certain conditions that some of the framework atoms maybe 5- or 6-coordinate. This may occur, for example, under conditions ofhydration when the composition of the material contains mainlyphosphorous and aluminum T-atoms. When this occurs it is found thatT-atoms may be also coordinated to one or two oxygen atoms of watermolecules (—OH₂), or of hydroxyl groups (—OH). For example, themolecular sieve AlPO₄-34 is known to reversibly change the coordinationof some aluminum T-atoms from 4-coordinate to 5- and 6-coordinate uponhydration as described by A. Tuel et al. in J. Phys. Chem. B 104, p.5697 (2000). It is also possible that some framework T-atoms can becoordinated to fluoride atoms (—F) when materials are prepared in thepresence of fluorine to make materials with 5-coordinate T-atoms asdescribed by H. Koller in J. Am. Chem. Soc. 121, p. 3368 (1999).

The invention also includes a method of synthesizing a crystallinesilicate composition of ITQ-26 having the diffraction pattern similar toTable 2 by mixing together a source of silica, organic structuredirecting agent (SDA), water, and optional metal, X, with a composition,in terms of mole ratios, within the following ranges:

R/YO₂ 0.01-1    H₂O/YO₂ 2-50 X/YO₂ 0-.2 and preferably within the following ranges:

R/YO₂ 0.1-.5  H₂O/YO₂ 5-20 X/YO₂ 0-.1 and X is any metal capable of tetrahedral coordination such as one ormore of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Be, Mn, As, In,Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capableof tetrahedral coordination, and even more preferably one or more of theelements B, Ga, Al, and Fe, and Y is Si alone or in combination with anyother tetravalent metal capable of tetrahedral coordination such as Geand Ti.

Said organic structure directing agent (SDA) is preferably1,3-bis-(triethylphosphoniummethyl)-benzene. See FIG. 1. Sources ofsilica can be colloidal, fumed or precipitated silica, silica gel,sodium or potassium silicates, or organic silicon such astetraethylorthosilicate, etc. Sources of metal can be boric acid,germanium (IV) ethoxide, germanium oxide, germanium nitrate, aluminumnitrate, sodium aluminate, aluminum sulfate, aluminum hydroxide,aluminum chloride and various salts of the metals X such as ironnitrate, iron chloride, and gallium nitrate, etc. The mixture is thenheated at a temperature and time sufficient to crystallize the silicate.

To the extent desired and depending on the X₂O₃/YO₂ molar ratio of thematerial, any cations present in the as-synthesized ITQ-26 can bereplaced in accordance with techniques well known in the art by ionexchange with other cations. Preferred replacing cations include metalions, hydrogen ions, and hydrogen precursor, e.g., ammonium ions andmixtures thereof. Particularly preferred cations are those which tailorthe catalytic activity for certain hydrocarbon conversion reactions.These include hydrogen, rare earth metals and metals of Groups IIA,IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of thePeriodic Table of the Elements.

The crystalline material of this invention can be used to catalyze awide variety of chemical conversion processes, particularly organiccompound conversion processes, including many of presentcommercial/industrial importance. Examples of chemical conversionprocesses which are effectively catalyzed by the crystalline material ofthis invention, by itself or in combination with one or more othercatalytically active substances including other crystalline catalysts,include those requiring a catalyst with acid activity.

Thus, in its active form ITQ-26 can exhibit a high acid activity, whichcan be measured with the alpha test. Alpha value is an approximateindication of the catalytic cracking activity of the catalyst comparedto a standard catalyst and it gives the relative rate constant (rate ofnormal hexane conversion per volume of catalyst per unit time). It isbased on the activity of silica-alumina cracking catalyst taken as anAlpha of 1 (Rate Constant=0.016 sec⁻¹). The Alpha Test is described inU.S. Pat. No. 3,354,078; in the Journal of Catalysis 4, 527 (1965); 6,278 (1966); and 61, 395 (1980), each incorporated herein by reference asto that description. The experimental conditions of the test used hereininclude a constant temperature of 538° C. and a variable flow rate asdescribed in detail in the Journal of Catalysis 61, 395 (1980).

When used as a catalyst, the crystalline material of the invention maybe subjected to treatment to remove part or all of any organicconstituent. This is conveniently effected by thermal treatment in whichthe as-synthesized material is heated at a temperature of at least about370° C. for at least 1 minute and generally not longer than 20 hours.While subatmospheric pressure can be employed for the thermal treatment,atmospheric pressure is desired for reasons of convenience. The thermaltreatment can be performed at a temperature up to about 927° C. Thethermally treated product, especially in its metal, hydrogen andammonium forms, is particularly useful in the catalysis of certainorganic, e.g., hydrocarbon, conversion reactions.

When used as a catalyst, the crystalline material can be intimatelycombined with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as, but not limited to, platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be in the composition by way of co-crystallization,exchanged into the composition to the extent a Group IIIA element, e.g.,aluminum, is in the structure, impregnated therein or intimatelyphysically admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating ITQ-26with a solution containing a platinum metal-containing ion. Thus,suitable platinum compounds for this purpose include chloroplatinicacid, platinous chloride and various compounds containing the platinumamine complex.

The crystalline material of this invention, when employed either as anadsorbent or as a catalyst in an organic compound conversion processshould be dehydrated, at least partially. This can be done by heating toa temperature in the range of 100° C. to about 370° C. in an atmospheresuch as air, nitrogen, etc., and at atmospheric, subatmospheric orsuperatmospheric pressures for between 30 minutes and 48 hours.Dehydration can also be performed at room temperature merely by placingthe ITQ-26 in a vacuum, but a longer time is required to obtain asufficient amount of dehydration.

As in the case of many catalysts, it may be desirable to incorporate thenew crystal with another material resistant to the temperatures andother conditions employed in organic conversion processes. Suchmaterials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides such as alumina. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Use of a material inconjunction with the new crystal, i.e., combined therewith or presentduring synthesis of the new crystal, which is active, tends to changethe conversion and/or selectivity of the catalyst in certain organicconversion processes. Inactive materials suitably serve as diluents tocontrol the amount of conversion in a given process so that products canbe obtained economically and orderly without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. Said materials, i.e., clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These clayand/or oxide binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, such as silica, zirconia, titania, magnesia, beryllia,alumina, and mixtures thereof.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided crystalline material andinorganic oxide matrix vary widely, with the crystal content rangingfrom about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 weight percent of the composite.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following example is presented.

EXAMPLE 1 Synthesis of ITQ-26

The germanium containing gel was prepared, according to the followingdescription: 0.62 of germanium oxide were dissolved in 24.19 g of asolution of 1,3-bis-(triethylphosphoniummethyl)-benzene hydroxide(FIG. 1) with a concentration of 0.62 mol of OH⁻ in 1000 g of solution.Then, 5.02 g of tetraethylorthosilicate were hydrolyzed in that solutionand the mixture was left to evaporate under stirring until completeevaporation of the ethanol formed was achieved. When the weight reached8.62 g of gel, 0.62 g of HF (48.1% wt.) were added and the mixture washomogenized. The final composition of the gel was:0.80Si0₂: 0.20Ge0₂: 0.25 m-B(Et₃P)₂(OH)₂: 0.50 HF: 7.50H₂0

The mixture was transferred to Teflon-lined stainless steel autoclavesand heated under stirring for 6 days at 175° C. Longer crystallizationtimes gave impure ITQ-26 with a small amount of polymorph C of Betazeolite.

The powder X-ray diffractogram of the sample as made and calcined isshown in FIG. 3 and FIG. 4 below. The sample was calcined in air to 550°C. for 3 hours, cooled down to 300° C., and then sealed under vacuum ina 2 mm quartz capillary tube to minimize structural damage.

The X-ray diffraction patterns are given in Table 6 and Table 7,respectively.

The porosity of the calcined material was measured by adsorbing nitrogenand argon. Adsorption measurements were carried out by manipulating thesample in an inert atmosphere. The results obtained are:

-   -   BET surface area: 257 m²/g    -   Micropore area: 243 m²/g    -   Micropore volume: 0.12 cm³/g    -   Pore diameter: 7.1 Å

That data suggest that ITQ-26 is a large pore (12-ring pore aperture)zeolite. This is confirmed by the structure discussed above.

EXAMPLE 2 Synthesis of ITQ-26

The germanium containing gel was prepared, according to the followingdescription: 0.75 of germanium oxide were dissolved in 22.5 g of asolution of 15% wt. 1,3-bis-(triethylphosphoniummethyl)-benzenehydroxide. Then, 6.01 g of tetraethylorthosilicate were hydrolyzed inthat solution and the mixture was left to evaporate under stirring untilcomplete evaporation of the ethanol formed was achieved. When the weightreached 10.3 g of gel, 0.74 g of HF (49% wt.) were added and the mixturewas homogenized. The final composition of the gel was:0.80 Si0₂: 0.20 Ge0₂: 0.25 m-B(Et₃P)₂(OH)₂: 0.50 HF: 7.50H₂0

The mixture was transferred to a Teflon-lined stainless steel autoclaveand heated for 6 days at 175° C. with a tumbling rate of 20 rpm. Thesample was recovered by filtration, washed with deionized water and thendried in an 115° C. oven. The X-ray diffraction pattern was measuredwith Cu Kα radiation and is similar to that given in Table 6 and FIG. 3.Analysis of the X-ray diffraction pattern showed the sample to be pureITQ-26.

TABLE 6 X-ray powder diffraction lines of as-made ITQ-26 (Cu Kαradiation) 2-Theta d (Å) I % 4.63 19.086 3 6.62 13.348 100 7.40 11.94419 9.43 9.376 8 9.92 8.907 60 10.47 8.440 3 11.94 7.407 6 13.70 6.460 2914.11 6.273 9 15.21 5.819 1 16.29 5.437 2 16.96 5.224 6 17.87 4.960 1018.83 4.709 25 19.98 4.441 37 20.26 4.379 5 21.34 4.160 79 22.99 3.866 123.30 3.815 5 23.39 3.801 1 23.53 3.779 23 24.29 3.661 30 25.30 3.518 626.08 3.414 5 26.72 3.334 54 27.57 3.233 8 28.54 3.125 6 29.98 2.979 1931.61 2.828 16 33.08 2.705 7 33.65 2.661 5 34.34 2.609 13 36.04 2.490 1437.08 2.423 8 38.20 2.354 16 40.65 2.218 8 43.52 2.078 8 46.32 1.959 648.38 1.880 4

TABLE 7 X-ray powder diffraction lines of calcined/dehydrated ITQ-26(Synchrotron radiation, λ = 0.8702 Å) 2-Theta d (A) I % 2.64 18.907 13.73 13.376 100 4.20 11.864 41 5.28 9.449 4 5.62 8.873 42 6.75 7.390 17.46 6.692 1 7.54 6.622 2 7.71 6.469 4 7.97 6.259 1 9.58 5.210 2 10.074.959 4 10.60 4.709 8 11.20 4.459 7 11.47 4.353 3 11.80 4.232 2 11.974.173 9 12.07 4.139 9 13.00 3.845 1 13.09 3.819 1 13.20 3.787 4 13.613.672 5 14.23 3.514 1 14.70 3.402 2 14.95 3.344 9 15.12 3.307 4 15.233.284 1 15.46 3.236 2 15.58 3.211 2 16.05 3.117 3 16.74 2.989 2 16.892.963 3 17.67 2.832 3 19.20 2.608 3 21.31 2.353 2

The invention claimed is:
 1. A synthetic crystalline material having aframework of tetrahedral atoms (T) connected by bridging atoms, thetetrahedral atom framework being defined by connecting the nearesttetrahedral (T) atoms in the manner shown in Table 1 of thespecification.
 2. The crystalline material of claim 1 wherein saidtetrahedral atoms include one or more elements selected from the groupconsisting of Li, Be, Al, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As,In, Sn, Sb, Ti, and Zr.
 3. The crystalline material of claims 1 or 2wherein said bridging atoms include one or more elements selected fromthe group consisting of O, N, F, S, Se, and C.
 4. A synthetic porouscrystalline material, as synthesized, characterized by an X-raydiffraction pattern including the peaks as substantially set forth inTable 2 of the specification.
 5. The crystalline material of claim 4wherein said crystalline material has a composition mR:aX₂O₃:YO₂.nH₂Owhere R is an organic compound, X is one or more metals selected fromthe group consisting of B, Ga, Al and Fe, and Y is one or more metalsselected from the group consisting of Si, Ge and Ti, and m is a realnumber less than or equal to 1, a is a real number less than or equal to0.2 and n is a real number less than or equal to
 10. 6. A calcineddehydrated material characterized by an X-ray diffraction patternincluding the most significant lines substantially, as set forth inTable 3 of the specification.
 7. The calcined dehydrated material ofclaim 6 wherein said crystalline material has a compositionaX₂O₃:YO₂.nH₂O where X is one or more metals selected from the groupconsisting of B, Ga, Al and Fe, and Y is one or more metals selectedfrom the group consisting of Si, Ge and Ti, and a is a real number lessthan or equal to 0.2 and n is a real number less than or equal to
 10. 8.A process for the separation of hydrocarbons from ahydrocarbon-containing stream using the material of claim
 6. 9. Aprocess for converting a feedstock comprising organic compounds to atleast one conversion product which comprises contacting said feedstockat organic compound conversion conditions with a catalyst comprising anactive form of the material of claim
 6. 10. The process for converting afeedstock of claim 9 wherein the catalyst is combined with ahydrogenating metal.
 11. The process for converting a feedstock of claim10 wherein said hydrogenating metal is one or more metals selected fromthe group consisting of tungsten, vanadium, molybdenum, rhenium, nickel,cobalt, chromium, manganese, or a noble metal.
 12. A method ofsynthesizing a crystalline silicate composition of ITQ-26 having thediffraction pattern substantially as set forth in Table 2 of thespecification by mixing together at least one source of silica, at leastone organic structure directing agent (R), water, and optionally asource of metal (X) to form a mixture having a composition, in terms ofmole ratios, within the following ranges: R/YO₂ 0.01-1    H₂O/YO₂ 2-50X/YO₂ 0-.2 

wherein X is any trivalent metal capable of tetrahedral coordination andY is silicon and optionally any other tetravalent metal capable oftetrahedral coordination.
 13. The method according to claim 12 wherein Xis one or more metals selected from the group consisting of B, Ga, Al orFe and Y is silicon and may include one or more metals selected from thegroup consisting of Ge and Ti.
 14. The method of claim 12 wherein saidmolar ratio ranges are R/YO₂ 0.1-.5  H₂O/YO₂ 5-20 X/YO₂ 0-.1 


15. A method of synthesizing a crystalline silicate composition of claim12 wherein said organic structure directing agent (SDA) is1,3-bis-(triethylphosphoniummethyl)-benzene.
 16. The crystallinesilicate composition produced using the method of claim
 12. 17. A methodof synthesizing a crystalline silicate composition of ITQ-26 having thediffraction pattern substantially as set forth in Table 2 of thespecification by mixing together a source of silica, organic structuredirecting agent (R), water, and optionally a source of metal (X), toform a mixture having a composition, in terms of mole ratios, within thefollowing ranges: R/YO₂ 0.01-1    H2O/YO₂ 2-50 X/YO₂ 0-.2 

and wherein X is one or more metals selected from the group consistingof B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti,and Zr, and Y is silicon and may include one or more metals selectedfrom the group consisting of Ge and Ti.